Purification method of aldehyde compound

ABSTRACT

A manufacturing method of an amine compound including obtaining a reaction solution containing an aldehyde compound by reacting a compound represented by Formula (a1) or (a2) with hydrogen and carbon monoxide in the presence of a metal compound of groups 8 to 10 and a phosphorus compound, neutralizing the reaction, purifying an aldehyde compound by distilling the neutralized reaction solution, and reacting the aldehyde compound with ammonia and with hydrogen in the presence of a catalyst to obtain an amine compound, wherein the phosphorus compound is represented by the Formula (R 1 O) 3 P, and the base compound is at least one selected from carbonate and hydrogen carbonate of metals of group I and carbonate and hydrogen carbonate of metals of group II, 
                         
and wherein the neutralizing the reaction solution is performed within a temperature range of 40° C. to 50° C.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/434,114, filed Apr. 8, 2015, which is a U.S. National StageApplication of PCT/JP2013/080315, filed Nov. 8, 2013, which claimspriority to Japanese Patent Application No. 2012-247464, filed Nov. 9,2012, the contents of all of which are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a purification method of a aldehydecompound, a manufacturing method of an aldehyde compound including thepurification method as a step, and a manufacturing method of an aminecompound and a manufacturing method of an isocyanate compound that usean aldehyde compound obtained by the aforementioned manufacturingmethod.

BACKGROUND ART

As a manufacturing method of an aldehyde compound using a norbornenecompound, for example, the methods described in Patent Documents 1 to 3are known.

Patent Documents 1 to 3 disclose methods for manufacturing formyl cyannorbornane by hydroformylating cyan norbornene by using a mixed gas ofH₂/CO in the presence of a catalyst. Patent Documents 1 and 2 disclosean example in which a metal compound is used as a catalyst. Herein,because a target compound can be obtained with a high degree ofselectivity, and a reaction pressure can be kept low, a rhodium complexis preferably used as a catalyst.

Patent Document 4 describes a metal ligand complex catalyst. In thisdocument, rhodium is exemplified as a metal, and an organic phosphorusligand is exemplified as a ligand.

Patent Document 5 discloses a method for treating a solution, whichcontains a trivalent phosphorus compound, a rhodium compound, and analdehyde compound, that is for recovering the rhodium metal. In thedocument, hydrolysis using water and a base compound such as NaOH isused.

RELATED DOCUMENT Patent Document

[Patent Document 1] Japanese Laid-open Patent Publication No. 57-193438

[Patent Document 2] Japanese Laid-open Patent Publication No. 60-72844

[Patent Document 3] U.S. Pat. No. 3,143,570

[Patent Document 4] Japanese Translation of PCT InternationalApplication No. 2003-505438

[Patent Document 5] Japanese Laid-open Patent Publication No. 6-49554

DISCLOSURE OF THE INVENTION

The present inventors found that when an amine compound is synthesizedby imino-hydrogenating an aldehyde compound, if a compound derived froma phosphorus compound used for a hydroformylation reaction remains,yield of the reaction is reduced. In order to improve the yield of thereaction, after the hydroformylation reaction, the obtained aldehydecompound and the compound derived from the phosphorus compound need tobe separated beforehand.

However, when the boiling point of the aldehyde compound is close to theboiling point of the compound derived from the phosphorus compound, itis difficult to separate the compounds by distillation in some cases.Furthermore, when the phosphorus compound is hydrolyzed such that it canbe separated by distillation, the solution becomes acidic, and thus thealdehyde compound loses stability in some cases. In addition, when theacidic solution obtained after the hydrolysis is neutralized with a basecompound so as to improve the stability of the aldehyde compound, thebase compound causes polymerization/decomposition of the aldehydecompound, and thus the stability deteriorates in some cases.

For this reason, the present invention aims to establish a purificationtechnique of an aldehyde compound that separates an aldehyde compoundand a compound derived from a phosphorus compound while maintainingstability of the aldehyde compound as a target substance.

As a result of performing intensive examination to solve the aboveproblem, the present inventors found a method for separating a compoundderived from a phosphorus compound while maintaining stability of analdehyde compound by using a predetermined base compound.

The present invention includes the following.

[1] A purification method of an aldehyde compound, including a step ofneutralizing a reaction solution containing an aldehyde compound byadding water and a base compound to the reaction solution, and a step ofdistilling the neutralized reaction solution, in which the reactionsolution is obtained by reacting a compound represented by the followingFormula (a1) or (a2) with hydrogen and carbon monoxide in the presenceof a metal compound of groups 8 to 10 and a phosphorus compound, thephosphorus compound is represented by the following Formula (R¹O)₃P, andthe base compound is at least one kind selected from among carbonate andhydrogen carbonate of metals of group I on the periodic table andcarbonate and hydrogen carbonate of metals of group II on the periodictable,

(in Formula (a1), X represents a hydrogen atom, a cyano group, analdehyde group, or a —CH═NR group; R represents a hydrogen atom, analkyl group having 1 to 6 carbon atoms, or an aryl group; and inFormulae (a1) and (a2), n represents 0, 1, or 2),(R¹O)₃P

(in the formula, a plurality of R¹s may be the same as or different fromeach other, and represents an alkyl group having 1 to 16 carbon atomsthat may have a substituent or an aryl group having 6 to 16 carbon atomsthat may have a substituent).

[2] The purification method of an aldehyde compound described in [1], inwhich the base compound is potassium hydrogen carbonate or potassiumcarbonate.

[3] The purification method of an aldehyde compound descried in [1] or[2], in which the phosphorus compound is at least one kind selected fromthe group consisting of triphenyl phosphite, trimethyl phosphite,triethyl phosphite, tripropyl phosphite, triisopropyl phosphite,trimethylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.

[4] The purification method of an aldehyde compound described in any oneof [1] to [3], in which the metal compound of groups 8 to 10 is arhodium compound, a cobalt compound, a ruthenium compound, or an ironcompound.

[5] The purification method of an aldehyde compound described in any oneof [1] to [3], in which the metal compound of groups 8 to 10 is arhodium compound.

[6] The purification method of an aldehyde compound described in any oneof [1] to [5], in which a compound represented by the Formula (a1) isused, and the compound is a compound represented by the followingFormula (1),

(in Formula (1), X has the same definition as X in Formula (a1)).

[7] The purification method of an aldehyde compound described in any oneof [1] to [6], in which the step of neutralizing the reaction solutionis performed within a temperature range of equal to or higher than 40°C. and equal to or lower than 50° C.

[8] A manufacturing method of an aldehyde compound, including a step ofobtaining a reaction solution containing an aldehyde compound byreacting a compound represented by the following Formula (a1) or (a2)with hydrogen and carbon monoxide in the presence of a metal compound ofgroups 8 to 10 and a phosphorus compound, a step of neutralizing thereaction solution by adding water and a base compound to the reactionsolution, and a step of purifying an aldehyde compound by distilling theneutralized reaction solution, in which the phosphorus compound isrepresented by the following Formula (R¹O)₃P, and the base compound isat least one kind selected from among carbonate and hydrogen carbonateof metals of group I on the periodic table and carbonate and hydrogencarbonate of metals of group II on the periodic table,

(in Formula (a1), X represents a hydrogen atom, a cyano group, analdehyde group, or a —CH═NR group; R represents a hydrogen atom, analkyl group having 1 to 6 carbon atoms, or an aryl group; and inFormulae (a1) and (a2), n represents 0, 1, or 2),(R¹O)₃P

(in the formula, a plurality of R¹s may be the same as or different fromeach other, and represents an alkyl group having 1 to 16 carbon atomsthat may have a substituent or an aryl group having 6 to 16 carbon atomsthat may have a substituent).

[9] The manufacturing method of an aldehyde compound described in [8],in which the base compound is potassium hydrogen carbonate or potassiumcarbonate.

[10] The manufacturing method of an aldehyde compound described in [8]or [9], in which the phosphorus compound is at least one kind selectedfrom the group consisting of triphenyl phosphite, trimethyl phosphite,triethyl phosphite, tripropyl phosphite, triisopropyl phosphite,trimethylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.

[11] The manufacturing method of an aldehyde compound described in anyone of [8] to [10], in which the metal compound of groups 8 to 10 is arhodium compound, a cobalt compound, a ruthenium compound, or an ironcompound.

[12] The manufacturing method of an aldehyde compound described in anyone of [8] to [10], in which the metal compound of groups 8 to 10 is arhodium compound.

[13] The manufacturing method of an aldehyde compound described in anyone of [8] to [12], in which a compound represented by the Formula (a1)is used, and the compound is a compound represented by the followingFormula (1),

(in Formula (1), X has the same definition as X in Formula (a1)).

[14] The manufacturing method of an aldehyde compound described in anyone of [8] to [13], in which the step of neutralizing the reactionsolution is performed within a temperature range of equal to or higherthan 40° C. and equal to or lower than 50° C.

[15] A manufacturing method of an amine compound, including a step ofreacting an aldehyde compound obtained by the manufacturing methoddescribed in any one of [8] to [14] with ammonia and with hydrogen inthe presence of a catalyst.

[16] A manufacturing method of an isocyanate compound, including a stepof reacting an amine compound obtained by the manufacturing methoddescribed in [15] with a carbonylating agent.

In the present invention, a “phosphorus compound” refers to a phosphoruscompound that can form a complex with a metal compound, and includes anyof a phosphorus compound having formed a complex with a metal compoundand a free phosphorus compound.

Furthermore, in the present invention, when a substance B is used in anamount of 1×10⁻⁶ mol with respect to 1 mol of a substance A, the amountof the substance B is described as 1 ppmmol.

Effect of the Invention

According to the purification method of an aldehyde compound of thepresent invention, it is possible to separate a compound derived from aphosphorus compound while maintaining stability of an aldehyde compound.Consequentially, it is possible to obtain an aldehyde compound, fromwhich the compound derived from the phosphorus compound has beenseparated and removed, while maintaining the yield.

The manufacturing method of an aldehyde compound, the manufacturingmethod of an amine compound, and the manufacturing method of anisocyanate compound using the amine compound obtained by theaforementioned manufacturing method of the present invention include thepurification method of an aldehyde compound as a step. Accordingly, themanufacturing methods are excellent in productivity and yield of thetarget compounds.

BRIEF DESCRIPTION OF THE DRAWINGS

The aforementioned object, other objects, characteristics, andadvantages become clearer by preferable embodiments described below andthe following drawings accompanied by the embodiments.

FIG. 1 is a ¹H-NMR chart of a compound obtained in Example 1.

FIG. 2 is a ¹H-NMR chart of a compound obtained in Example 6.

FIG. 3 is a ¹H-NMR chart of a compound obtained in Example 7.

DESCRIPTION OF EMBODIMENTS

Hereinafter, a manufacturing method of an aldehyde compound, amanufacturing method of an amine compound, and a manufacturing method ofan isocyanate compound of the present embodiment will be described inthis order. Herein, a purification method of an aldehyde compound of thepresent embodiment will be described in the manufacturing method of analdehyde compound.

<Manufacturing Method of Aldehyde Compound>

The manufacturing method of an aldehyde compound of the presentembodiment includes a step of reacting a compound represented by thefollowing Formula (a1) or (a2) with hydrogen and carbon monoxide in thepresence of a metal compound of groups 8 to 10 and a predeterminedphosphorus compound.

In Formula (a1), X represents a hydrogen atom, a cyano group, analdehyde group, or a —CH═NR group, and R represents a hydrogen atom, analkyl group having 1 to 6 carbon atoms, or an aryl group. X ispreferably a cyano group or an aldehyde group, and more preferably acyano group. In Formulae (a1) and (a2), n represents 0, 1, or 2. n ispreferably 0 or 1, and more preferably 1.

The compound represented by Formula (a1) may be any of an endo-isomerand an exo-isomer, or may be a mixture containing these isomers at anyratio.

Specific examples of the compound represented by Formula (a1) includethe following compounds.

(1) Examples of the compound in which n is 0 include cyclohexene,4-cyano-1-cyclohexene, 3-cyclohexene-1-carboxyaldehyde, and4-iminomethyl-1-cyclohexene.

(2) Examples of the compound in which n is 1 includebicyclo[2.2.1]-2-heptene, bicyclo[2.2.1]-5-heptene-2-carbonitrile,bicyclo[2.2.1]-5-heptene-2-carboxyaldehyde, andbicyclo[2.2.1]-5-hepten-2-yl methanamine.

(3) Examples of the compound in which n is 2 includebicyclo[2.2.2]-2-octene, bicyclo[2.2.2]-5-octene-2-carbonitrile,bicyclo[2.2.2]-5-octene-2-carboxyaldehyde, andbicyclo[2.2.2]-5-hepten-2-yl methanamine.

Examples of the compound represented by Formula (a2) include thefollowing compounds.

(1) Examples of the compound in which n is 0 include 1,4-cyclohexadiene.

(2) Examples of the compound in which n is 1 includebicyclo[2.2.1]hepta-2,5-diene.

(3) Examples of the compound in which n is 2 includebicyclo[2.2.2]octa-2,5-diene.

In the present embodiment, it is preferable to use the compoundrepresented by Formula (a1), and it is more preferable for n to be 1.Specifically, as such a compound, a compound represented by thefollowing Formula (1) can be preferably used.

In Formula (1), X has the same definition as X in Formula (a1). X ispreferably a cyano group or an aldehyde group, and more preferably acyano group.

Herein, the compound represented by Formula (1) may be any of anendo-isomer and an exo-isomer, and may be a mixture containing theseisomers at any ratio.

The metal compound of groups 8 to 10 used in the reaction of the presentembodiment is a rhodium compound, a cobalt compound, a rutheniumcompound, or an iron compound.

Examples of the rhodium compound include Rh(acac)(CO)₂, Rh(acac)₃,RhCl(CO) (PPh₃)₂, RhCl(PPh₃)₃, RhBr(CO) (PPh₃)₂, Rh₂(CO)₈, Rh₄(CO)₁₂,Rh₆(CO)₁₆, and the like. Examples of the cobalt compound includeHCo(CO)₃, HCo(CO)₄, Co₂(CO)₈, HCo₃(CO)₉, and the like. Examples of theruthenium compound include Ru(CO)₃(PPh₃)₂, RuCl₂(PPh₃)₃, RuCl₃ (PPh₃)₃,Ru₃(CO)₁₂, and the like. Examples of the iron compound include Fe(CO)₅,Fe(CO)₄PPh₃, Fe(CO)₄(PPh₃)₂, and the like. Herein, “acac” meansacetylacetonate.

The rhodium compound used in the reaction of the present embodiment isnot particularly limited as long as it is a compound containingmonovalent rhodium metal, and examples thereof include rhodium carbonylcatalysts such as dicarbonyl acetylacetonate rhodium (Rh(acac)(CO)₂),dodecacarbonyl tetrarhodium (Rh₄(CO)₁₂), hexadecacarbonyl hexarhodium(Rh₆(CO)₁₆), and octacarbonyl rhodium (Rh₂(CO)₈); rhodium chloride; andthe like.

The phosphorus compound used in the reaction of the present invention isrepresented by the following Formula.(R¹O)₃P

In the formula, a plurality of R¹s may be the same as or different fromeach other, and represents an alkyl group having 1 to 16 carbon atomsthat may have a substituent or an aryl group having 6 to 16 carbon atomsthat may have a substituent.

Examples of the substituent of the alkyl group having 1 to 16 carbonatoms or the aryl group having 6 to 16 carbon atoms include an alkylgroup having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbonatoms, an alkenyl group having 1 to 6 carbon atoms, a hydroxyl group, anamino group, a cyano group, and the like.

In the present embodiment, R¹ is preferably an aryl group having 6 to 16carbon atoms that may have a substituent.

Specific examples of the phosphorus compound include trivalentphosphorus compounds such as triphenyl phosphite, trimethyl phosphite,triethyl phosphite, tripropyl phosphite, triisopropyl phosphite,trimethylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.One kind of these can be used singly, or two or more kinds thereof canbe used in combination.

A hydroformylation reaction using these raw materials can be performedsuch that it satisfies the following condition (1), the condition (2),and/or the condition (3). In the present embodiment, it is preferablefor the reaction to satisfy two conditions including the condition (1)and the condition (2).

(1) The amount of the metal of groups 8 to 10 included in the metalcompound of groups 8 to 10 is 0.01 ppmmol to 300 ppmmol, preferably 0.15ppmmol to 100 ppmmol, more preferably 0.5 ppmmol to 100 ppmmol, andparticularly preferably 1 ppmmol to 100 ppmmol, with respect to 1 mol ofthe compound represented by Formula (a1) or (a2).

(2) A molar ratio of the phosphorus compound (mol)/the metal of groups 8to 10 (mol) contained in the metal compound of groups 8 to 10 is equalto or greater than 100, preferably equal to or greater than 150, andmore preferably equal to or greater than 200. The upper limit thereof isnot particularly limited. However, from the viewpoint of theaforementioned effects, the upper limit is equal to or less than1,000,000, preferably equal to or less than 100,000, more preferablyequal to or less than 50,000, and particularly preferably equal to orless than 10,000. The lower limit and the upper limit can be combined inany way.

(3) A molar ratio of the phosphorus compound (mol)/the compoundrepresented by Formula (a1) or (a2) (mol) is 0.003 to 0.05, preferably0.003 to 0.03, and more preferably 0.003 to 0.02.

Herein, the range of the numerical values of the conditions (1) to (3)can be combined in any way.

The method satisfying such conditions can achieve excellent productivityof an aldehyde compound and can obtained high yield, even when theamount of the metal of groups 8 to 10 is reduced. Presumably, becausethe amount of the phosphorus compound used is increased, the activity ofthe metal compound of groups 8 to 10 is improved more than expected,hence the aforementioned effects are obtained. It is also consideredthat the compound represented by Formula (a1) or (a2) exerts a strongsteric or electronic influence, hence the aforementioned effects areobtained.

Specifically, an aldehyde compound can be synthesized in the followingmanner.

First, a rhodium compound, a phosphorus compound, and the compound as araw material represented by Formula (a1) or (a2) are put into a reactor.Then hydrogen and carbon monoxide gas are supplied into the reactor, andin this state, a hydroformylation reaction can be performed at atemperature of 30° C. to 120° C. under a pressure of 0.1 MPa to 1.0 MPafor a reaction time of 1 hour to 8 hours. Herein, a uniform reactionsystem including only an oil phase or a double layer reaction systemincluding a water layer and an oil layer can be appropriately selectedto perform the hydroformylation reaction.

In this way, the compound represented by Formula (a1) or (a2) ishydroformylated, and an aldehyde compound is synthesized.

The hydroformylation reaction can be performed without using a solvent,and can use a substituted or unsubstituted aromatic compound, asubstituted or unsubstituted aliphatic hydrocarbon compound, or analcohol. The hydroformylation reaction can be performed in a solventsuch as toluene, benzene, hexane, octane, acetonitrile, benzonitrile,o-dichlorobenzene, ethanol, pentanol, or octanol. The hydroformylationreaction of the present embodiment exhibits excellent reactivity at ahigh concentration. Accordingly, the hydroformylation reaction can beperformed without using a solvent. As a result, a step of evaporating asolvent and the like become unnecessary, hence the reaction is performedby a simple step. Furthermore, the volume efficiency is improved, andthe production efficiency becomes excellent.

By the manufacturing method of the present embodiment, an aldehydecompound represented by the following Formula (b1) is synthesized fromthe compound of Formula (a1). Moreover, from the compound of Formula(a2), an aldehyde compound represented by the following Formula (b2) issynthesized.

When n is 1 or 2, and X is a group other than a hydrogen atom, thecompound represented by Formula (b1) or (b2) can be obtained in the formof either a “compound in which the 2-position and the 5-position havebeen substituted with a predetermined group (hereinafter, the compoundwill be referred to as a “2,5-isomer”)” or a “compound in which the2-position and the 6-position have been substituted with a predeterminedgroup (hereinafter, the compound will be referred to as a“2,6-isomer”)”, or can be obtained in the form of a mixture containingthese isomers at any ratio. Depending on the steric configuration of thesubstituent, each of the 2,5-isomer and the 2,6-isomer can be obtainedin any form including an endo-endo isomer, an endo-exo-isomer, and anexo-exo-isomer, or can be obtained in the form of a mixture containingat least two kinds of these isomers at any ratio.

Herein, when n is 0, and X is a group other than a hydrogen atom, thecompound represented by Formula (b1) or (b2) can be obtained in the formof either a cis-isomer or a trans-isomer, or can be obtained in the formof a mixture containing these isomers as any ratio.

In Formula (b1) or (b2), X and n have the same definition as X inFormula (a1) or (a2).

In the present embodiment, the compound represented by Formula (b1) ispreferably obtained, and examples of such a compound include a compoundrepresented by the following Formula (2).

In Formula (2), X has the same definition as X in Formula (1).

Herein, the aldehyde compound represented by Formula (2) can be obtainedin the form of either a “compound in which the 2-position ofbicyclo[2.2.1]heptane has been substituted with the substituent X andthe 5-position thereof has been substituted with an aldehyde group(hereinafter, the compound will be referred to as a “2,5-isomer”)” or a“compound in which the 2-position has been substituted with thesubstituent X and the 6-position has been substituted with an aldehydegroup (hereinafter, the compound will be referred to as a“2,6-isomer”)”, or can be obtained in the form of a mixture containingthese isomers at any ratio. Furthermore, depending on the stericconfiguration of the substituent, each of the 2,5-isomer and the2,6-isomer can be obtained in any form including an endo-endo isomer, anendo-exo-isomer, and an exo-exo-isomer, or can be obtained in the formof a mixture containing at least two kinds of these isomers at anyratio.

After the hydroformylation reaction ends, a target aldehyde compound canbe obtained by performing a purification step which will be describedlater.

<Purification Method of Aldehyde Compound>

The purification method of an aldehyde compound of the presentembodiment includes a step of neutralizing a reaction solution, whichcontains the aldehyde compound obtained as above, by adding water andthe following base compound to the reaction solution, and a step ofdistilling the neutralized reaction solution.

The reaction solution which contains the aldehyde compound contains thealdehyde compound represented by the Formula (b1) or (b2), a phosphoruscompound, and a compound containing rhodium. In the present embodiment,the “compound containing rhodium” also includes any of a compound in theform of a complex consisting of the rhodium compound added as a rawmaterial, the phosphorus compound, CO/H₂ and a free rhodium compound.

When water and a base compound are added to the reaction solution, waterand an aqueous solution of a base compound may be added, or only asolution containing a base compound may be added.

The amount of water to be mixed is 2.0% by mass to 10.0% by mass,preferably 5.0% by mass to 9.0% by mass, more preferably 6.0% by mass to9.0% by mass, with respect to the total amount of the solution of themixture. This is the total amount of water and water of the aqueoussolution of a base compound.

In the present embodiment, the base compound used in the reaction is atleast one kind selected from among carbonate and hydrogen carbonate ofmetals of group I on the periodic table and carbonate and hydrogencarbonate of metals of group II on the periodic table.

Examples of the base compound include sodium hydrogen carbonate, sodiumcarbonate, potassium hydrogen carbonate, potassium carbonate, calciumcarbonate, magnesium carbonate, and the like.

Herein, at a point in time when the base compound has been added, insome cases, a reaction product (impurities) derived from the basecompound and the phosphorus compound is precipitated, or alternatively,a reaction product (impurities) is precipitated similarly to the stillresidue remaining after distillation. Accordingly, from the viewpoint ofindustrial process, it is preferable to use potassium hydrogen carbonateor potassium carbonate as the base compound. If such bases containingpotassium are used, the precipitation of the aforementioned reactionproduct (impurities) can be inhibited.

Particularly, potassium carbonate exhibits high solubility in water andmakes it possible to prepare a high-concentration aqueous solution.Potassium carbonate can increase neutralization efficiency from theviewpoint described above, and availability thereof is high. Therefore,it can also be suitably used for mass production.

Specifically, purification of an aldehyde compound can be performed asbelow.

A mixture of a compound containing rhodium, a phosphorus compound, and acompound represented by Formula (b1) or (b2) is put into a reactor. Thenwater is added thereto, and the resultant is treated for a reaction timeof 2 hours to 10 hours under normal pressure at a temperature of 40° C.to 80° C., preferably at 40° C. to 50° C.

Thereafter, an aqueous solution of a base compound was added thereto toperform a neutralization treatment. The conditions of the neutralizationtreatment can be appropriately set according to the manufacturing scaleand the like. However, the neutralization treatment is preferablyperformed within a temperature range of equal to or higher than 40° C.and equal to or lower than 50° C. Furthermore, the pressure condition ispreferably set to be a normal pressure, and the neutralization ispreferably performed for a reaction time of 1 hour to 2 hours.

Moreover, in the present embodiment, after the neutralization treatment,distillation and purification are performed under a reduced pressure.

By these steps, it is possible to suitably separate a compound derivedfrom a phosphorus compound while maintaining stability of the aldehydecompound represented by Formula (b1) or (b2). Consequentially, it ispossible to obtain an aldehyde compound, from which a compound derivedfrom a phosphorus compound has been separated and removed, whilemaintaining the yield of the aldehyde compound obtained by the precedingstep.

In addition, in the purification step of the present embodiment, afterwater is added and a heating treatment is performed, an aqueous solutionof a base compound is added. At this time, if the aqueous solution of abase compound is added within the aforementioned temperature range, itis possible to efficiently neutralize the reaction system without theneed to excessively cool the reaction system. That is, if neutralizationis performed within the aforementioned temperature range, it is possibleto improve the production efficiency while maintaining stability of thealdehyde compound.

The manufacturing method of an amine compound of the present embodimentthat will be described later and the manufacturing method of anisocyanate compound using an amine compound obtained by theaforementioned manufacturing method includes the purification method ofan aldehyde compound as a step. Accordingly, the manufacturing methodsare excellent in productivity and yield of the target compounds.

<Manufacturing Method of Amine Compound>

The manufacturing method of an amine compound of the present embodimentincludes the following steps.

Step (a): a step of reacting a compound represented by the Formula (a1)or (a2) with hydrogen and carbon monoxide in the presence of a metalcompound of groups 8 to 10 and a phosphorus compound

Step (b): a step of reacting an aldehyde compound obtained by Step (a)with ammonia and with hydrogen in the presence of a catalyst

The manufacturing method of an amine compound of the present embodimentincludes the aforementioned manufacturing method of an aldehyde compoundas in Step (a). Therefore, in Step (a), the productivity and yield ofthe aldehyde compound are excellent, and as a result, the productivityand yield of an amine compound as a target compound also becomeexcellent.

Herein, because Step (a) is the same as the step in the “manufacturingmethod of an aldehyde compound”, description of this step will not berepeated.

In step (b), the aldehyde compound represented by the Formula (b1) or(b2) that is obtained by Step (a) is iminated by being reacted withammonia, and hydrogen is added thereto in the presence of a catalyst. Inthis way, an amine compound is synthesized.

As the catalyst, a metal catalyst such as nickel, platinum, palladium,or ruthenium, and the like can be used. When the aldehyde compound has acyano group as a substituent, a —CH₂—NH₂ group is generated by hydrogenreduction.

In this way, in Step (b), the aldehyde group of the aldehyde compoundbecomes an amino group by imination, and the cyano group also becomes anamino group by hydrogen reduction. Consequentially, an amine compoundrepresented by the following Formula (c1) having two amino groups issynthesized. Herein, when the aldehyde compound represented by Formula(b1) in which X is a hydrogen atom is used, an amine compoundrepresented by the following Formula (c2) is synthesized.

In Formula (c1) or (c2), n has the same definition as n in Formula (a1)or (a2).

When n is 1 or 2, the compound represented by Formula (c1) can beobtained in the form of either a “compound in which the 2-position andthe 5-position have been substituted with a predetermined group(hereinafter, the compound will be referred to as a “2,5-isomer”)” or a“compound in which the 2-position and the 6-position have beensubstituted with a predetermined group (hereinafter, the compound willbe referred to as a “2,6-isomer”)”, or can be obtained in the form of amixture containing these isomers at any ratio. Furthermore, depending onthe steric configuration of the substituent, each of the 2,5-isomer andthe 2,6-isomer can be obtained in any form including anendo-endo-isomer, an endo-exo-isomer, and an exo-exo-isomer, or can beobtained in the form of a mixture containing at least two kinds of theseisomers at any ratio.

Herein, when n is 0, the compound represented by Formula (c1) can beobtained in the form of either a cis-isomer or a trans-isomer, or can beobtained in the form of a mixture containing these isomers as any ratio.

When n is 1 or 2, the compound represented by Formula (c2) can beobtained in the form of either an endo-isomer or an exo-isomer, or canbe obtained in the form of a mixture containing these isomers at anyratio.

The compound of Formula (c1) is preferably obtained, and examples ofsuch a compound include a compound of the following Chemical formula (3)in which n is 1.

The amine compound represented by Chemical formula (3) can be obtainedin the form of either a “compound in which the 2-position and the5-position of bicyclo[2.2.1]heptane have been substituted with anaminomethyl group (hereinafter, the compound will be referred to as a“2,5-isomer”)” or a “compound in which the 2-position and the 6-positionhave been substituted with an aminomethyl group (hereinafter, thecompound will be referred to as a “2,6-isomer”), or can be obtained inthe form of a mixture containing these isomers at any ratio.Furthermore, depending on the steric configuration of the substituent,each of the 2,5-isomer and the 2,6-isomer can be obtained in any formincluding an endo-endo-isomer, an endo-exo-isomer, and anexo-exo-isomer, or can be obtained in the form of a mixture containingat least two kinds of these isomers at any ratio.

Specifically, the aforementioned imination and hydrogenation reactioncan be performed in the following manner. First, an aldehyde compound, asolvent, and a catalyst are put into a reactor, and ammonia gas is blowninto the reactor. Then hydrogen is injected into the reactor at apressure of up to about 1 MPa; the reactor is heated up to about 100°C.; and while hydrogen is being supplied into the reactor, a reaction isperformed for about 1 hour to 10 hours at the aforementioned temperatureand pressure. As the solvent, for example, an alcohol having 1 to 8carbon atoms, water, or the like is suitably used.

After the reaction ends, by performing filtration of catalyst,desolvation, a purification step, and the like as in a typical case, atarget amine compound can be obtained.

<Manufacturing Method of Isocyanate Compound>

The manufacturing method of an isocyanate compound of the presentembodiment includes the following steps.

Step (a): a step of reacting a compound represented by the Formula (a1)or (a2) with hydrogen and carbon monoxide in the presence of a metalcompound of groups 8 to 10 and a phosphorus compound

Step (b): a step of reacting an aldehyde compound obtained by Step (a)with ammonia and with hydrogen in the presence of a catalyst

Step (c): a step of reacting an amine compound obtained by Step (b) witha carbonylating agent

The manufacturing method of an isocyanate compound of the presentembodiment includes the aforementioned manufacturing method of analdehyde compound as Step (a). Therefore, in Step (a), the productivityand yield of the aldehyde compound are excellent, and as a result, theproductivity and yield of an isocyanate compound as a target compoundalso become excellent.

Herein, Step (a) is the same as the step in the “manufacturing method ofan aldehyde compound”, and Step (b) is the same as the step in the“manufacturing method of an amine compound”. Therefore, description ofStep (a) and Step (b) will not be repeated.

In Step (c), the amine compound represented by Formula (c1) or (c2)obtained by Step (b) is reacted with a carbonylating agent underpredetermined conditions, whereby an isocyanate compound represented bythe following Formula (d1) or (d2) is synthesized. As the carbonylatingagent, phosgene, a urea derivative, a carbonate derivative, carbonmonoxide, or the like can be used.

n in Formula (d1) or (d2) has the same definition as n in Formula (a1)or (a2).

When n is 1 or 2, the compound represented by Formula (d1) can beobtained in the form of either a “compound in which the 2-position andthe 5-position have been substituted with a predetermined group(hereinafter, the compound will be referred to as a “2,5-isomer”)” or a“compound in which the 2-position and the 6-position have beensubstituted with a predetermined group (hereinafter, the compound willbe referred to as a “2,6-isomer”)”, or can be obtained in the form of amixture containing these isomers at any ratio. Furthermore, depending onthe steric configuration of the substituent, each of the 2,5-isomer andthe 2,6-isomer can be obtained in any form including anendo-endo-isomer, an endo-exo-isomer, and an exo-exo-isomer, or can beobtained in the form of a mixture containing at least two kinds of theseisomers at any ratio.

Herein, when n is 0, the compound represented by Formula (d1) can beobtained in the form of either a cis-isomer or a trans-isomer, or can beobtained in the form of a mixture containing these isomers at any ratio.

When n is 1 or 2, the compound represented by Formula (d2) can beobtained in the form of an endo-isomer or an exo-isomer, or can beobtained in the form of a mixture containing these isomers at any ratio.

The compound represented by Formula (d1) is preferably obtained, andexamples of such a compound include a compound represented by thefollowing Chemical formula (4) in which n is 1.

Herein, the isocyanate compound represented by Chemical formula (4) canbe obtained in the form of either a “compound in which the 2-positionand the 5-position of bicyclo[2.2.1]heptane have been substituted withan isocyanatomethyl group (hereinafter, the compound will be referred toas a “2,5-isomer”)” or a “compound in which the 2-position and the6-position have been substituted with an isocyanatomethyl group(hereinafter, the compound will be referred to as a “2,6-isomer”)”, orcan be obtained in the form of a mixture containing these isomers at anyratio. Furthermore, depending on the steric configuration of thesubstituent, each of the 2,5-isomer and the 2,6-isomer can be obtainedin any form including an endo-endo-isomer, an endo-exo-isomer, and anexo-exo-isomer, or can be obtained in the form of a mixture containingat least two kinds of these isomers at any ratio.

When phosgene is used as the carbonylating agent, specific examples ofStep (c) include a method in which an amine compound and a solvent areput into a reactor first, and the amine compound is made into an aminehydrochloride by using hydrochloric acid and then reacted with phosgene;a method in which the amine compound is directly reacted with phosgeneso as to obtain a carbamoyl chloride compound, and then the compound isthermally decomposed; and the like. Furthermore, after the reactionends, by performing a purification step and the like as in a typicalcase, a target isocyanate compound can be obtained.

When phosgene is used as a carbonylating agent, the reaction solvent isnot particularly limited. However, it is preferable to use an organicaromatic compound having a high boiling point or an ester compound thatexhibits high solubility in hydrochloric acid at the time of asalt-forming reaction and exhibits high solubility in phosgene and lowsolubility in hydrochloric acid at the time of a phosgenation reaction.Examples of the organic aromatic compound having a high boiling pointinclude 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene,isopropylbenzene, 1,2,4-trimethylbenzene, amylbenzene, diamylbenzene,triamylbenzene, dodecylbenzene, p-cymene, cumene methylphenyl ether,ethylphenyl ether, diisoamyl ether, n-hexylether, o-dichlorobenzene,p-chlorotoluene, bromobenzene, 1,2,4-trichlorobenzene, and the like.Furthermore, the ester compound is not particularly limited, but aceticacid esters such as isoamyl acetate and isooctyl acetate are preferable.Among the solvents exemplified above, an aromatic halogen compound isparticularly preferable as the solvent for embodying the presentembodiment.

The isocyanate compound obtained by the present embodiment can be usedas a raw material of optical materials and a coating material. Moreover,the amine compound obtained by the present embodiment can be used as acoating material and a raw material of curing agents.

EXAMPLE

Hereinafter, the present invention will be more specifically describedbased on examples and the like, but the scope of the present inventionis not limited to the examples and the like.

Reference Example Synthesis of bicyclo[2.2.1]-5-heptene-2-carbonitrile

195.0 g (1.40 mol) of dicyclopentadiene having purity of 95% and 163.6(3.08 mol) of acrylonitrile to which 0.36 g (1.8 mmol) ofN-nitrosodiphenylamine was added were put into a 1,000 ml autoclave. Thecomponents were reacted for 5 hours at 160° C. while being stirred andthen heated to 180° C. and reacted for 2 hours, and the reaction ended.In this way, 355.6 g of a reaction liquid containingbicyclo[2.2.1]-5-heptene-2-carbonitrile was obtained. As a resultanalysis, it was confirmed that the reaction liquid contained 331.2 g(2.78 mol) of bicyclo[2.2.1]-5-heptene-2-carbonitrile. 352.4 g of theobtained reaction liquid containing 328.2 g (2.75 mol) ofbicyclo[2.2.1]-5-heptene-2-carbonitrile was put into a 500 mL flask andsubjected to distillation under reduced pressure, thereby obtaining300.7 g (2.52 mol) of bicyclo[2.2.1]-5-heptene-2-carbonitrile as a mainfraction.

Manufacture Example 1 Synthesis of 2-cyano-5-formylbicyclo[2.2.1]heptaneand 2-cyano-6-formylbicyclo[2.2.1]heptane

3.7 mg (0.014 mmol) of rhodium dicarbonyl acetylacetonate, 168.73 g (1.4mol) of bicyclo[2.2.1]-5-heptene-2-carbonitrile obtained in referenceexample, 4.45 g (14.3 mmol) of triphenyl phosphite, and 59.0 g oftoluene were put into an electromagnetic stirring-type autoclave made ofSUS316L having an internal volume of 0.5 L, and the components werestirred at 25° C., thereby obtaining 232.2 g of a liquid preparation ofa Rh catalyst. Herein, conditions (1) to (3) were as follows.

-   -   Amount of rhodium used (condition (1)): amount of rhodium        contained in rhodium dicarbonyl acetylacetonate was 10 ppmmol        with respect to 1 mol of        bicyclo[2.2.1]-5-heptene-2-carbonitrile.    -   Amount of phosphorus compound used (a) (condition (2)):        triphenyl phosphite (mol)/rhodium contained in rhodium        dicarbonyl acetylacetonate (mol): 1,000    -   Amount of phosphorus compound (b) (condition (3)):        triphenylphosphite (mol)/bicyclo[2.2.1]-5-heptene-2-carbonitrile        (mol): 0.01

Thereafter, the autoclave was thoroughly purged with nitrogen and thenthoroughly purged with a mixed gas of carbon monoxide/hydrogen=50/50(volume ratio). The same gas was injected into the autoclave until theinternal pressure became 0.6 MPaG, and then the autoclave was heated to100° C. to start a hydroformylation reaction. In process of thereaction, the internal pressure of the autoclave decreases. Therefore,the mixed gas was continuously supplied such that the internal pressurewas kept at 0.6 MPaG, and the liquid temperature was regulated to bekept at 80° C. In this state, the reaction was performed for 6 hours.After the reaction ended, the mixed gas in the system was purged withnitrogen, thereby obtaining 241.0 g of a reaction liquid containing2-cyano-5,(6)-formylbicyclo[2.2.1]heptane. As a result of analyzing thereaction liquid, it was confirmed that the reaction liquid contained208.8 g (1.4 mol) of 2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane.

The same operation was repeated for 10 times, thereby obtaining a totalof 2410.0 g of a reaction liquid containing 2088.0 g (14.0 mol) of2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane.

Example 1 Purification of 2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane

263.8 g of a solution (containing 228.6 g (1.53 mol) of2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane) from the reaction liquid obtainedin Manufacture example 1 and 14.0 g of water were put into a four-neckreaction flask having an internal volume of 2 L equipped with a refluxcondenser tube, a stirring blade, and a thermometer. The components wereheated to 40° C. while being stirred and then stirred for 10 hours. As aresult of analyzing the obtained solution, it was confirmed that thesolution contained 228.6 g (1.53 mol) of2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane, but triphenyl phosphite was notdetected.

6.4 g (0.012 mol) of a 20% by weight of aqueous potassium hydrogencarbonate solution was added dropwise to the mixed solution within atemperature range of 40° C. to 45° C. until pH of the solution became7.0, and the solution was stirred for 1 hour to 2 hours.

Subsequently, the solution was distilled and purified under reducedpressure, thereby obtaining 235.9 g of a solution containing 222.9 g(1.49 mol) of 2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane (yield 97.5%). A ¹H-NMR chartthereof is shown in FIG. 1.

After the solution was distilled under reduced pressure, the stillresidue was visually checked. As a result, precipitation of a salt wasnot observed. The results are shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 3

An aldehyde compound was purified in the same manner as in Example 1,except that the aqueous potassium hydrogen carbonate solution used forneutralization was replaced with a 20% by weight aqueous solution of thebase compound shown in Table 1. The results are shown in Table 1.

Example 6 Synthesis of 2,5-bisaminomethyl-bicyclo[2.2.1]heptane and2,6-bisaminomethyl-bicyclo[2.2.1]heptane

89.5 g (0.6 mol) of 2-cyano-5-formylbicyclo[2.2.1]heptane and2-cyano-6-formylbicyclo[2.2.1]heptane obtained in Example 1, 89.5 g ofmethanol, and 4.5 g (dry mass) of a Raney cobalt catalyst (cobalt: 94%by mass, aluminum: 3.5% by mass, manganese: 2.1% by mass) obtained bydeveloping a cobalt-aluminum alloy containing manganese were put into anelectromagnetic stirring-type autoclave made of stainless steel havingan internal volume of 0.5 L, and 24.5 g (1.44 mol) of ammonia gas wasblown into the autoclave.

Thereafter, the autoclave was thoroughly purged with nitrogen and thenpurged with hydrogen. Then hydrogen was injected into the autoclaveuntil the internal pressure became 1.2 MPaG, and the components wereheated to 100° C. while being stirred, thereby starting a reaction. Inprocess of the reaction, the internal pressure of the autoclavedecreases. Therefore, hydrogen was continuously supplied such that thepressure was kept at 1.2 MPaG, and the liquid temperature was regulatedto be kept at 100° C. In this state, the hydrogenation reaction wasperformed for 6 hours.

The autoclave was cooled to room temperature, the Raney cobalt catalystwas removed by filtration, and then ammonia and methanol were evaporatedat 60° C. and 4 kPa, thereby obtaining 102.0 g of a solution containing2,5-bisaminomethyl-bicyclo[2.2.1]heptane and2,6-bisaminomethyl-bicyclo[2.2.1]heptane.

102.0 g of the solution containing2,5-bisaminomethyl-bicyclo[2.2.1]heptane and2,6-bisaminomethyl-bicyclo[2.2.1]heptane was put into a 200 ml flask,and the solution was distilled under reduced pressure, thereby obtaining79.0 of a mixture of purified 2,5-bisaminomethyl-bicyclo[2.2.1]heptaneand 2,6-bisaminomethyl-bicyclo[2.2.1]heptane. A ¹H-NMR chart thereof isshown in FIG. 2. The same operation was repeated twice, therebyobtaining 158 g of a mixture of purified2,5-bisaminomethyl-bicyclo[2.2.1]heptane and2,6-bisaminomethyl-bicyclo[2.2.1]heptane.

Example 7 Synthesis of 2,5-bisisocyanatomethyl-bicyclo[2.2.1]heptane and2,6-bisisocyanatomethyl-bicyclo[2.2.1]heptane

958 g of o-dichlorobenzene was put into a five-neck flask having aninternal volume of 2 L equipped with a reflux condenser tube, a stirringblade, a thermometer, a gas blowing tube, and a raw material inlet tube.Furthermore, 154.2 g (1.0 mol) of2,5-bisaminomethy-bicyclo[2.2.1]heptane and2,6-bisaminomethy-bicyclo[2.2.1]heptane obtained in Example 6 and 702 gof o-dichlorobenzene were put into a raw material tank. Thereafter, thereactor was heated to 120° C. at 0.1 MPa, and then injection ofhydrochloric acid gas from a hydrochloric acid blowing tube at a rate of43.8 g/hr and injection of amine, which was diluted with a solvent inthe raw material tank, from a raw material injection pump at a rate of428.1 g/hr were started at the same time, and the entirety of thehydrochloric acid gas and amine were injected into the reactioncontained over 2 hours. Furthermore, while hydrochloric acid gas wasbeing injected at a rate of 20 g/hr, the resultant was aged for 1 hour.After the reaction ended, a reaction mass of hydrochloride was heated to160° C., then phosgene was blown into the reactor at 100 g/hr (1.0mol/hr) from a phosgene blowing tube, and a reaction was performed for 6hours while maintaining the temperature. After the reaction ended, theunreacted phosgene and hydrochloric acid gas in the system were purgedwith nitrogen, and desolvation was performed, thereby obtaining 200.9 gof a solution containing 2,5-bisisocyanatomethyl-bicyclo[2.2.1]heptaneand 2,6-bisisocyanatomethyl-bicyclo[2.2.1]heptane. Furthermore, thesolution was distilled under reduced pressure, thereby obtaining 175.7 gof a mixture of 2,5-bisisocyanatomethyl-bicyclo[2.2.1]heptane and2,6-bisisocyanatomethyl-bicyclo[2.2.1]heptane having purity of 99.0%. A¹H-NMR chart thereof is shown in FIG. 3.

The above examples describe the case of obtaining a mixture of acompound (2,5-isomer) in which the 2-position and the 5-position ofbicyclo[2.2.1]heptane have been substituted and a compound (2,6-isomer)in which the 2-position and the 6-position have been substituted.However, depending on the reaction conditions, either the 2,5-isomer orthe 2,6-isomer can be obtained. Moreover, depending on the stericconfiguration of the substituent, the 2,5-isomer can be obtained in anyform including an endo-endo-isomer, an endo-exo-isomer, and an exo-exoisomer, or can be obtained in the form of a mixture containing at leasttwo kinds of these isomers at any ratio. Likewise, the 2,6-isomer can beobtained in any form including an endo-endo-isomer, an endo-exo-isomer,and an exo-exo-isomer, or can be obtained in the form of a mixturecontaining at least two kinds of these isomers.

TABLE 1 Yield of aldehyde Precipitation of Base compound compound: %salt Example 1 KHCO₃ 97.5 Not occurred Example 2 K₂CO₃ 95.7 Not occurredExample 3 NaHCO₃ 95.8 Occurred Example 4 Na₂CO₃ 96.6 Occurred Example 5CaCO₃ 93.5 Occurred Comparative NaOH 19.9 Occurred example 1 ComparativeKOH 25.6 Not occurred example 2 Comparative Ca(OH)₂ 36.3 Occurredexample 3

In Examples 1 to 5, the aldehyde compound could be obtained at highyield of equal to or greater than 90%. In contrast, in Comparativeexamples 1 to 3, the aldehyde compound was obtained at low yield ofequal to or less than 50%. Moreover, in Examples 1 and 2, precipitationof impurities derived from the base compound and the phosphorus compoundwas not observed in the still residue, and it showed that the presentinvention is industrially useful.

The present application claims priority based on Japanese PatentApplication No. 2012-247464 filed on Nov. 9, 2012, the entire content ofwhich is incorporated herein.

The invention claimed is:
 1. A manufacturing method of an aminecompound, comprising: a step of obtaining a reaction solution containingan aldehyde compound by reacting a compound represented by the followingFormula (a1) or (a2) with hydrogen and carbon monoxide in the presenceof a metal compound of groups 8 to 10 and a phosphorus compound; a stepof neutralizing the reaction solution by adding water and a basecompound to the reaction solution; a step of purifying an aldehydecompound by distilling the neutralized reaction solution; and a step ofreacting the aldehyde compound with ammonia and with hydrogen in thepresence of a catalyst to obtain an amine compound, wherein thephosphorus compound is represented by the following Formula (R¹O)₃P,wherein in the formula, a plurality of R¹s may be the same as ordifferent from each other, and represents an alkyl group having 1 to 16carbon atoms that may have a substituent or an aryl group having 6 to 16carbon atoms that may have a substituent, and wherein the base compoundis potassium hydrogen carbonate,

in Formula (a1), X represents a hydrogen atom, a cyano group, analdehyde group, or a —CH═NR group; R represents a hydrogen atom, analkyl group having 1 to 6 carbon atoms, or an aryl group; and inFormulae (a1) and (a2), n represents 0, 1, or 2, and wherein the step ofneutralizing the reaction solution is performed within a temperaturerange of equal to or higher than 40° C. and equal to or lower than 50°C.
 2. The manufacturing method of an amine compound according to claim1, wherein the phosphorus compound is at least one selected from thegroup consisting of triphenyl phosphite, trimethyl phosphite, triethylphosphite, tripropyl phosphite, triisopropyl phosphite, trimethylphenylphosphite, and tris(2,4-di-tert-butylphenyl) phosphite.
 3. Themanufacturing method of an amine compound according to claim 1, whereinthe metal compound of groups 8 to 10 is a rhodium compound, a cobaltcompound, a ruthenium compound, or an iron compound.
 4. Themanufacturing method of an amine compound according to claim 1, whereinthe metal compound of groups 8 to 10 is a rhodium compound.
 5. Themanufacturing method of an amine compound according to claim 1, whereina compound represented by the Formula (a1) is used, and the compound isa compound represented by the following Formula (1),

in Formula (1), X has the same definition as X in Formula (a1).